An unusual equilibrium chlorine atom transfer process and its potential for assessment of steric pressure by bulky
Rhett C Smith1, Shashin Shah, Eugenijus Urnezius
1Department of Chemistry, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106-7078, USA.
Abstract:
An unusually facile intermolecular chlorine atom transfer process has been discovered between the phospha-Wittig reagents ArP=PMe3 and ArPCl2 (Ar is a sterically hindered aryl group). The atom transfer process is catalyzed by added PMe3. A mechanism is forwarded that is based upon a Me3P/Me3PCl2 couple that allows shuttling of chlorine atoms between ArP groups. This unique transfer process is exploited to evaluate the steric properties of aryl groups via an equilibrium process.
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